Metal-boron derivatives as lubricant additives

ABSTRACT

Boron and/or metal-boron derivatives having extreme pressure anti-wear and friction reducing properties and lubricating compositions containing the same are disclosed. The lubricating compositions comprise a major amount of a lubricating oil and a minor amount of an extreme pressure, anti-wear and friction reducing additive comprising a boramid or metal containing boramid compound.

RELATED APPLICATIONS

This application is a divisional of application Ser. No. 158,828, filedJune 12, 1980, now U.S. Pat. No. 4,400,284.

FIELD OF THE INVENTION

This invention relates to lubricating oils, and more particularly toanti-wear, friction reducing and extreme pressure lubricating oils andadditives therefor. Anti-wear, friction reducing and extreme pressure(or "E.P.") additives, as they are commonly called, are chemicals whichare added to lubricating compositions to reduce friction and reduce orprevent destructive metal-to-metal contact in the lubrication of movingsurfaces. Lubricating oils provide good lubrication between movingsurfaces in contact with each other, as long as a film of said oil ismaintained between the relatively moving surfaces. This particular kindof lubrication is commonly termed "hydrodynamic lubrication". However,when pressure and/or rubbing speeds between moving metal surfaces aresuch that the film of lubricating oil is no longer intact,metal-to-metal contact and wear occur over a significant portion of thepreviously lubricated area. Under such conditions, a kind of lubricationcalled boundary lubrication is needed, and is governed by parameters ofthe contacting surfaces, such as, surface finish, hardness, metal shearstrength, and the coefficient of friction between the metals involved.Destructive metal-to-metal contact, due to lack of lubrication underextreme conditions, manifests itself in different forms such as scoring,welding, scuffing, ridging, rippling, rapid wear, and in some casesdeformation or complete destruction of the metal components.

Extreme pressure, anti-wear and friction reducing lubricating additivesprevent destructive metal-to-metal contact, under boundary lubricationconditions, by adsorption or reacting with relatively moving metalsurfaces to form an adherent, protective film of compounds which have alower shear strength than that of the metal surfaces. This film acts inthe capacity of a "boundary lubricant" and performs the function oflubrication when metal-to-metal contact occurs. Boundary conditions andboundary lubricant refer to the conditions and a suitable lubricantrelating to the combination of applied load, fluid viscosity and rubbingspeed, which do not allow hydrodynamic lubrication to exist.Hydrodynamic lubrication exists when a film of lubricant maintainsseparation between lubricated surfaces.

Many extreme pressure and anti-wear agents are oil soluble or easilydispersed as a stable dispersion in oil. Many of the E.P. agents whichprovide the high load capacity are chemically reactive, containingchlorine, sulfur or phosphorus which react with metal surfaces.

It has now been discovered that certain oil-soluble or dispersible boronor metal-boron derivatives prepared as described herein, when added tolubricating oils or grease not only improve the ability of the lubricantto prevent seizure of the parts being lubricated but in addition greatlyreduce the amount of friction and wear of such moving parts. We havesynthesized a new family of extreme pressure and anti-wear compoundswhich are boron derivatives and/or reaction products of "boramids", andmetal salts thereof, as described further herein.

DESCRIPTION OF THE PRIOR ART

The use of boron containing compounds as extreme pressure and anti-wearadditives for lubricating oils is known and appreciated by the priorart. For example, U.S. Pat. No. 3,313,727 to Peeler disclosescompositions of amorphous alkali metal borates as a stable dispersion inlubrication oils. In particular, a boron compound, such as, themetaborates and tetraborates of sodium and potassium in combination witha lyophilic surface active agent, such as, the carboxylates, phenatesand sulfonates of alkaline earth metals, e.g. calcium and barium, whendispersed in lubrication oil compositions are said to improve theextreme pressure and anti-wear properties thereof.

U.S. Pat. No. 2,987,476 to Hartley et al. relates to a method forsolubilizing boric acid and metal borates in liquid fuels for internalcombustion engines and in lubricating oils and greases. Desirablecompositions are prepared by hydrolyzing an organic ester of boric acidin the presence of three materials, namely, a lyophilic ionic surfaceactive agent, a non-polar organic liquid and a water-miscible organicliquid. The resulting dispersible boron-containing product of thisprocess is a complex of an inorganic boric acid compound with anoleophilic ionic surface active agent.

Another boron composition is disclosed in U.S. Pat. No. 3,598,855 toCyba which relates to cyclic borates of polymeric alkanolamines formedby reacting a borylating agent with a polymeric alkanolamine. Theadditives thus formed are described as additives for a wide variety ofpetroleum products including lubricating oils.

U.S. Pat. No. 3,227,739 to Versteeg relates to lubricating oilscontaining additives formed by reacting certain amine type compoundswith boric acid. The amine type compounds are prepared by reacting equalmolar proportions of diethanol-amine or dipropanolamine and a long chain1,2-epoxide.

Another extreme pressure lubrication composition is disclosed in U.S.Pat. No. 3,185,644 to Knowles et al., which relates to lubricatingcompositions containing amine salts of boron-containing compounds. Theamine salts are formed by reaction of a hydroxy substituted amine and atrihydrocarbyl borate. The amine-borate compounds thus formed aredescribed as useful as load carrying additives for mineral and syntheticbase lubricating oils.

From the foregoing, it can readily be seen that there is an ongoingsearch for extreme pressure, anti-wear and friction reducing lubricatingcompositions which contain boron and/or metal-boron derivates.

SUMMARY OF THE INVENTION

This invention resides in an extreme pressure, anti-wear, and frictionreducing lubrication composition comprising a major amount of alubricating oil and a minor amount of an extreme pressure, anti-wearadditive of the formula: ##STR1## wherein R is hydrogen, alkyl, cyclic,alicyclic, aryl, alkylaryl, or arylalkyl radicals having from 1 to about24 carbon atoms, R' and R" are straight or branched carbon chains,cyclic, alicyclic, aryl, alkylaryl or arylalkyl radicals having from 2to about 20 carbon atoms, Y is an integer of 1 to 4, and X is eitherhydrogen, a transition metal having an atomic number between 21 and 30or a Group IVA metal of the Periodic Table and mixtures thereof.

DESCRIPTION OF THE INVENTION

The present invention resides in extreme pressure, anti-wear andfriction reducing lubricating oil compositions comprising a major amountof an oil of lubrication viscosity and as an extreme pressure andanti-wear additive a minor amount of a boron or metal-boron derivativeas described hereinbelow.

The terms "friction reducing and anti-wear" herein refer to the abilityof a substance to reduce the coefficient of friction between sliding orrubbing surfaces and/or the ability of a substance to preventmetal-to-metal welding or bonding during rubbing at extremely highcontact pressures. "Extreme pressure lubricant" refers to a fluid orother substance which provides lubrication during extreme pressureconditions, including boundary lubrication. The term boramid denotes thereaction product of a primary amine, an alkylene oxide or epoxide andboric acid, all of which are further described herein. Metal derivativesof boramids are the reaction product of the desired metal and specifiedboramid compound.

The extreme pressure and anti-wear additives described herein may beincorporated in a wide variety of lubricating oils, for example, mineraloil, (including automobile engine oil), crude oil, synthetic oil,industrial oils, for example, cutting oil, metal working fluids andgrease. For example, the additives may be added to lubricating oilsderived from paraffins, naphthenic or mixed base crude petroleum oils,that have been subjected to solvent and/or sulfuric-acid treatment,aluminum chloride treatment, hydrogenation and/or other refiningtreatments. In addition, the additives described herein may beincorporated in petroleum distillates, such as diesel fuel, jet enginefuel, furnace oil, gas oil and other light oils. The petroleum oils maybe of virgin or cracked petroleum stock, or mixtures thereof, boiling inthe range of about 100° F. to about 1,100° F. The petroleum oil maycontain cracked components such as those derived from cycle oils orcycle cuts boiling above gasoline, usually in the range of about 450° F.to about 750° F. and may be derived by catalytic or thermal cracking.Oils of high or low sulfur content such as diesel fuels or oils mayadditionally be used.

Preferred distillate lubrication oils which are improved by the additionof additives herein have an initial boiling point within the range of350° F. to about 475° F., an end point in the range of about 500° F. toabout 1,100° F., and a flash point not lower than 110° F.

Lubricants derived from oil shale are particularly desirable for useherein. Oil shale is broadly defined as a variety of compact sedimentaryrock, generally laminated, that contains little or no oil but doescontain organic material, derived from aquatic organisms or waxy sporesand pollen grains, which is convertible to oil by heat. Crude shale oil,in combination with water, gas and spent shale containing a carbonaceousresidue and mineral matter, is formed by the pyrolysis of oil shale. Thehydrocarbons of shale oil are highly unsaturated, resembling theproducts of thermal cracking of petroleum, as would be expected becauseof the pyrolytic origin of shale oil. Once the shale oil is extracted,it is subjected to conventional hydrotreating procedures to produce avariety of hydrocarbon products, including lubricants.

Synthetic lubricating oils as defined herein are those oils derived froma product of chemical synthesis (man-made oils). Typical examples ofsuch compositions include the polyglycol fluids (i.e., polyalkyleneglycol); silicones which consist of a silicone-oxygen polymer chain towhich are attached hydrocarbon branches composed of either alkyl orphenyl groups; phosphates; polyphenyl esters; synthetic hydrocarbons andvarious esters of organic acids and alcohols.

The polyalkylene glycol lubricating oils suitable for use hereinpreferably are derived from the reaction product of the appropriatealkylene oxides. The alkylene moiety of the above compositions have acarbon chain of from about 1 to about 10 carbon atoms, preferably fromabout 2 to about 7 carbon atoms and a molecular weight within the rangeof from about 200 to about 2,000, especially from about 200 to about1,000, most preferably from about 200 to about 800. Representativeexamples of suitable polyalkylene glycols include, polyethylene glycol,polypropylene glycol, polyisopropylene glycol, polybutylene glycol andthe like.

Silicone lubricants have extra-ordinary low viscosity-temperaturecoefficients coupled with good oxidation stability. The lubricantcontains a repeating silicon-oxygen backbone and has organic groups R,wherein R is methyl, phenyl, vinyl and the like. The silicones hereinhave an average molecular weight within the range of from about 400 toabout 9,000.

The polyphenyl ethers suitable for use herein have from 3 to 7 benzenerings and from 1 to 6 oxygen atoms, with the stated oxygen atoms joiningthe stated benzene rings in chains as ether linkages. One or more of thestated benzene rings in these polyphenyl ethers may behydrocarbonyl-substituted. The hydrocarbonyl substituents, for thermalstability, must be free of CH and aliphatic CH so that preferredaliphatic substituents are lower saturated hydrocarbon radicals (1 to 6carbon atoms) like methyl and tert-butyl, and preferred aromaticsubstituents are aryl radicals like phenyl and tolyl. In the lattercase, the benzene ring supplied in the hydrocarbonyl substituentcontributes to the total number of benzene rings in the molecule.Polyphenyl ethers consisting exclusively of chains of from 3 to 7benzene rings with at least one oxygen atom joining the stated benzenerings in the chains as an ether linkage have particularly desirablethermal stability.

Exemplary of the alkyl polyphenyl ethers suitable for use are 3-ringpolyphenyl ethers like 1-(p-methylphenoxy) 4-phenoxybenzene and2,4-diphenoxy-1-methyl-benzene, 4-ring polyethers like bis[p-(p-methyl-phenoxy)phenyl] ether and bis [(p-tert-butylphenoxy)phenyl] ether, and the like.

Polyphenyl ethers consisting exclusively of benzene rings and etheroxygen atoms linking said rings are exemplified by the triphenoxybenzenes and aryl-substituted polyphenyl ethers such as biphenylphenoxyphenyl ether, biphenylyloxyphenyl phenoxyphenyl ether, biphenylylether, dibiphenylyloxybenzene, bis(phenylyloxyphenyl) ether, and thelike.

A preferred class of polyphenyl ethers comprises those consisting ofbenzene rings joined in a chain by oxygen atoms as ether linkagesbetween each ring. Examples of the polyphenyl ethers contemplated in theclass are the bis(phenoxy-phenyl)ethers (4 benzene rings joined in achain by 3 oxygen atoms), illustrative of which is bis(m-phenoxyphenyl)ether. The bis(phenoxy-phenoxy) benzenes are particularly preferred inthe present invention. Illustrative of these arem-bis(m-phenoxy-phenoxy) benzene, m-bis(p-phenoxy-phenoxy) benzene,o-bis(o-phenoxy-phenoxy) benzene, and so forth. Further, the polyphenylethers suitable for use herein include the bis(phenoxy-phenoxy-phenyl)ethers such as bis[m-(m-phenoxy-phenoxy) phenyl] ether,bis[p-(p-phenoxy-phenoxy phenyl] ether, m-(m-phenoxy-phenoxy) phenylm-(o-phenoxy-phenoxy) phenyl ether and the bis (phenoxy-phenoxy-phenoxy)benzenes such as m-bis[m-phenoxy-phenoxy-phenoxy] benzene,p-bis[p-(m-phenoxy-phenoxy) phenoxy] benzene andm-bis[m-p-phenoxy-phenoxy) phenoxy] benzene.

Synthetic lubricating oils derived from hydrocarbons are generally oftwo types, namely, dialkylated benzene and polymerized alpha-olefins.Dialkylated benzene herein is formed from the condensation product ofthe appropriate alkyl compound and has a carbon chain from about 5 toabout 50 carbon atoms, preferably from about 8 to about 20 carbon atoms;and a molecular weight of from about 200 to about 1,500, preferably fromabout 300 to about 700. Representative compounds includedi-n-decylbenzene, n-decyl-n-tetradecylbenzene, andn-nonyl-n-dodecylbenzene.

Alpha-olefins suitable for use in preparing lubricating oils herein arecharacterized by the formula RCH═CH.sub. 2, wherein R is a radicalselected from the group of hydrogen and alkyl radicals having from about4 to about 18 carbon atoms, preferably from about 6 to about 10 carbonatoms, and having a molecular weight of from about 80 to about 300,preferably from about 100 to about 200. Typical compounds include1-octene, 1-decene and 1-dodecene.

Phosphates suitable for use herein as synthetic lubricating oils are thephosphate esters having the formula O═P(OR)₃, wherein R is aryl or alkylhaving from about 4 to about 20 carbon atoms, preferably from 6 to about10 carbon atoms, and have a molecular weight within the range of fromabout 200 to about 1,000, preferably from about 300 to about 550.Representative compounds include trioctyl phosphate, tricresyl phosphateand dicresyl methyl phosphate.

Esters of organic acids which are suitable for use herein as syntheticlubricating oils preferably are selected from organic acids havingcarbon chains of from C₄ to C₄₀ carbon units. Organic acids which may bereacted with the alcohols herein include caproic, decanoic, sebacic,laurel, oleic, stearic, palmitic etc. Likewise, alcohols herein may bederived from either natural or synthetic origin for example,pentaerythritol, trimethylolpropane, amyl, 2-ethylhexanol or laurelalcohol, may be used to form the desired ester. The esters are formedusing conventional methods. For example, the esters may be prepared byreaction of the desired alcohol with the desired acid, acid anhydride oracid halide using conventional reaction conditions and techniques.

Synthetic lubricating oils which are improved by the addition of theadditives herein additionally include those derived from solidcarbonaceous products, conveniently prepared by blending finely groundcarbonaceous materials with a solvent to form a slurry. The slurry isthen introduced into a reaction vessel containing a conventionalhydrogenation catalyst and is reacted under normal hydrogenatingpressures and temperatures. After hydrogenation, solids that are presentmay conveniently be removed from the product stream. The product is nextstripped of solvent. The balance of the product stream may be distilledto obtain products of various boiling ranges, for example, hydrocarbonsboiling in the gasoline range and hydrocarbons boiling in thelubricating oil range. Some of the products are useful as fuels andoils, the remainder may be further treated by a conventional petroleumprocess including cracking, hydrocracking, and the like. Syntheticlubricating oils produced from solid carbonaceous products, such ascoal, are primarily aromatic and generally have a boiling range of about300° F. to about 1,400° F., a density of about 0.1 to about 1.1 and acarbon to hydrogen molecular ratio in the range of about 1.3:1 to about0.66:1. A typical example is a lubricating oil obtained from asubbituminous coal, such as Wyoming-Montana coal, comprising a middleoil having a boiling range of from about 375° F. to about 675° F. Adescription of how to prepare synthetic lubricating oils from acarbonaceous material, for example coal, is set forth in greater detailin U.S. Pat. No. 3,957,619 issued to Chun et al. on May 18, 1976, thedisclosure of which is incorporated herein by reference.

Alternatively, the synthetic oil improved herein may be a nonhydrocarbonoil of lubricating viscosity. Suitable examples include synthetic oilsobtained by polymerization of lower molecular weight alkylene oxides,such as propylene oxide and/or ethylene oxide employing alcohol or acidinitiators, such as lauryl alcohol or acetic acid. Other typicalsynthetic oils include esters, for example, di(2-ethylhexyl)-silicate,tricresylphosphate and silicate esters, such astetra-(2-ethyl-hexyl)-orthosilicate and hexa-(2-ethylbutoxy)-disiloxane.

If desired, the extreme pressure, anti-wear and friction reducingadditives described herein may be employed in conjunction with otheradditives commonly used in petroleum products. Thus, there may be addedto the oil compositions of this invention rust and corrosion inhibitors,emulsifying agents, antioxidants, dyes, haze inhibitors, anti-staticagents, detergents, dispersants, viscosity index improvement agents andpour point reducing agents. Soaps or other thickening agents may beadded to the lubricating oil compositions to form compositions havingthe consistency of a grease. When other additives are employed, it maybe desirable, although not necessary to prepare additive concentratescomprising concentrated solutions of the herein boron or metal-boronderivatives together with said other additives whereby the severaladditives are added simultaneously. Dissolution of the additive oradditive concentrate into the oil composition may be facilitated bymixing accompanied with mild heating, but this is not absolutelyessential.

Metal-working fluids such as cutting and grinding fluids are defined asliquids applied to a cutting tool or apparatus to assist in a cutting ormachining process by washing away chips or serving as a lubricant orcoolant, for example, in milling, drilling, turning, cutting, threading,broaching, surface grinding, form grinding, flute grinding, and similarmetal-working operations. These oils are preferably obtained fromconventionally refined lubricating oils containing film-strengthadditives, or sulfurized napthene-base oils which may additionallycontain emulsifying agents. Representative fluids and agents include:water, water solutions or emulsions of detergents and oils, mineraloils, fatty oils, chlorinated mineral oils, sulfurized mineral oils andmixtures thereof.

The herein described extreme pressure, anti-wear and friction reducingadditives may be incorporated in the lubricating oils in any convenientway. Thus, the boron or metal-boron derivatives may be added directly tothe oil by dissolving the desired boron derivative in the lubricatingoil at the desired level of concentration.

Normally, the additive comprising boron or metal-boron derivatives isblended with the lubricating oil from about 0.1 to about 15 percent byweight, preferably from about 0.5 to about 10 percent by weight of theoil composition. Alternatively, the additive may be blended withsuitable solvents to form concentrates that may readily be dissolved inthe appropriate oil at the desired concentration. If a concentrate isemployed, it ordinarily will contain at least 10 to about 65 percent byweight of the additive and preferably from 25 to about 65 percent byweight of said additive. The solvent in such a concentrate may bepresent in amounts of about 35 to about 75 percent by weight. Suitablesolvents which may be used for this purpose are naphtha, and lightmineral oil (i.e., 150 neutral to 450 neutral) and mixtures thereof. Theparticular solvent selected should, of course, be selected so as not toadversely affect the other desired properties of the ultimate oilcomposition. Thus, the solvent for use in incorporating the additive ina fuel oil should be compatible with the fuel in terms of stability,boiling range, corrosiveness, etc.

The extreme pressure, anti-wear additives of the present invention arerepresented by the following formula: ##STR2## wherein R is hydrogen,alkyl, cyclic, alicyclic, aryl, alkylaryl, or arylalkyl radicals havingfrom 1 to about 24 carbon atoms, preferably from 1 to about 18 carbonatoms, R' and R" are straight or branched carbon chains, cyclic,alicyclic, aryl, alkyaryl, or arylalkyl radicals having from 2 to about20 carbon atoms, especially from about 2 to about 10 carbon atoms, y isan integer from 1 to 4, and X is either hydrogen or a metal selectedfrom transition metals having an atomic number between 21 and 30 or aGroup IVA metal of the Periodic Table and mixtures thereof.

The above group of compounds, including metal derivatives thereof arereferred to as boramids. The above compounds are conveniently preparedby reacting a primary amine with an alkylene oxide or epoxide. Theresulting product is, then reacted with boric acid to give thecorresponding boramid compound. Amines which are suitable for use hereininclude methylamine, ethylamine, propylamine, butylamine,octadecylamine, dodecylamine, cyclohexylamine, phenylamine, cocoamine,tallowamine and oleylamine and mixtures thereof. A wide variety ofalkene oxides or epoxides may be used to prepare the precursor for theboramid compounds herein. Typical alkene oxides or epoxides which aresuitable for use include ethylene oxide, propylene oxide,1,2-epoxybutane, cyclohexene oxide, cyclooctene oxide, cyclododeceneoxide, and 1,2-epoxybenzene and mixtures thereof. Normally, the boronatom will comprise from about 0.5 to about 10 weight percent, especiallyfrom about 2 to about 5 weight percent of the boramid compound. Theboramid and/or metal-boramid compounds produced in accordance with theprocedure herein are preferably selected from the group comprisingmethylaminodiethylate hydrogen borate, ethylaminodiethylate hydrogenborate, propylaminodiethylate hydrogen borate, butylaminodiethylatehydrogen borate, octadecylaminodiethylate hydrogen borate,dodecylaminodiethylate hydrogen borate, cyclohexylaminodiethylatehydrogen borate, phenylaminodiethylate hydrogen borate,oleylaminodiethylate hydrogen borate, cocoaminodiethylate hydrogenborate, and tallowaminodiethylate hydrogen borate and mixtures thereof.

It should be noted that a transition metal having an atomic numberbetween 21 and 30 or a Group IVA metal of the Periodic Table may beincorporated into the boramid compounds herein. When a transition metalis incorporated into said compound, the metal component will replace thehydrogen atom on the hydroxy portion of the structure. In addition, theExamples, as set forth hereinafter, recite cocoaminodiethylate hydrogenborate as boramid C/12, tallowaminodiethylate hydrogen borate as boramidT/12 and octadecylaminodiethylate hydrogen borate as boramid 18/12. Thecorresponding metal-boron derivatives will, of course, incorporate thedesired metal into the composition before the boramid nomenclature, forexample, zinc boramid C/12, etc.

Metals are conveniently incorporated into the boramid compound usingconventional methods and apparatus. Normally, the metal is reacted withthe desired boramid compound in salt form. Thus the metal acetates,propanates, hexanates etc. are suitable for use. It should be noted thatnot all metal salts are desirable for incorporating the metal ion intothe boramid compound. The metal carbonates, nitrates, oxalates,chlorides, sulfates, hydroxides and oxides, to name a few, are allundesirable as vehicles for imparting metal ions into the boramidcompound. These metal salts experience solubility problems, separationproblems and in addition, undesirable ions are frequently left in theboramid compound.

Desirable metals are conveniently selected from first row transitionmetals of the Periodic Table. Transition metals which are suitable foruse are selected from scandium, titanium, vanadium, chromium, manganese,iron, cobalt, nickel, copper, zinc and mixtures thereof. Group IVAmetals which are useful herein include tin and lead and mixturesthereof. Normally, the metal will comprise from about 1 to about 17weight percent, preferably from about 5 to about 10 weight percent ofthe boramid compound.

Generally, when two different boramid compounds or derivatives thereofare blended together, a weight ratio of from about 1:20 to about 20:1,preferably from about 1:10 to about 10:1 is highly desirable forimparting extreme pressure, anti-wear and friction reducing propertiesto a lubricant.

The invention will be further described with reference to the followingExamples.

EXAMPLE I

A boramid compound is prepared by adding 20 grams of boric acid, 95grams of Armak Ethomeen C/12 [bis (2-hydroxyethyl) cocoamine] and 250 mlof tolune to a single-necked one liter round-bottomed flask. The tolueneacts as a solvent and as an azeotrope for water produced during thereaction. It should be noted that boric acid is not soluble in tolueneor Ethomeen C/12. The flask is placed in a heating mantle and fittedwith a Dean-Stark trap that is topped with a condenser. The mixture thusformed is, then, heated until it begins to reflux. Next, the mantle isadjusted to give a moderate reflux rate. The reaction mixture isrefluxed for one hour, or until the stoichiometric amount of water (12ml.) collects in the Dean-Stark trap and all of the boric acid hasdissolved, after which the toluene is distilled from the reactionproduct. The reaction product (103 grams) is designated boramid C/12 andhas a clear golden color. Boramid C/12 is a fluid liquid while hot butsets into a soft viscous material when cooled to room temperature. Thecompound is readily soluble in hydrocarbon solvents and water.

EXAMPLE II

A boramid compound is prepared by following the procedure of Example Iwith the following substitution:

Armak Ethomeen T/12 [bis (2-hydroxyethyl) tallowamine] is substitutedfor the Armak Ethomeen C/12. Substantially the same results areobtained, however, the resulting compound is designated boramid T/12.

EXAMPLE III

A boramid compound is prepared by mixing 20 grams of boric acid, 95grams of Armak Ethomeen 18/12 [bis (2-hydroxyethyl) octadecylamine] and,as a solvent, 250 ml of toluene in a single-necked one literround-bottomed flask. The flask is placed in a heating mantle and fittedwith a Dean-Stark trap and water cooled condenser. The mixture is heatedunder reflux for one hour, during which 12 ml of water collects in theDean-Stark trap. The toluene is then distilled from the reactionproduct. The compound is designated boramid 18/12 and is readily solublein hydrocarbon solvents and water.

EXAMPLE IV

The procedure of Example III is followed to prepare a boramid compoundwith the following exception: N,N-diethanol-n-methylamine (46.3 grams)is substituted for the Armak Ethomeen 18/12. The reaction product thusproduced is a liquid product with the consistency of honey when hot andbecomes a waxy semi-solid when cooled to room temperature.

EXAMPLE V

Boric acid (20 grams), N,N-diethanol-N-phenylamine (46.3 grams) and 250mls of toluene are mixed in a one liter single-necked flask to prepare aboramid compound. The flask is equipped with a heating mantle,Dean-Stark trap and water-cooled condenser. The mixture is heated underreflux until the reaction is completed (12 ml of water collects),approximately one hour, and the toluene is distilled from the reactionmixture. The product thus prepared is suitable for use as an extremepressure, antiwear and friction reducing additive for lubricationcompositions.

EXAMPLE VI

A metal derivative of boramid C/12 is prepared by mixing 54 grams of theproduct of Example I (boramid C/12), 400 ml of toluene, 24.6 grams ofnickel acetate and 150 ml of methanol in a single-necked, one literround bottom flask which is equipped with a heating mantle andwater-cooled condenser. The mixture is refluxed for four hours. Next,water, toluene, methanol and acetic acid are distilled from the reactionproduct. The product (59 grams) contained 7.8 weight percent nickel asdetermined by emission spectroscopy and the resulting product is a fluidgreen liquid when hot, which turns into a solid upon cooling to roomtemperature. The product is readily soluble in hydrocarbon solvents andwater.

EXAMPLE VII

A metal boramid is prepared by following the procedure of Example IIwith the following exception: the boramid T/12 (54 grams), 400 ml oftoluene, 24 grams of nickel acetate and 150 mls of methanol are mixed ina single-necked, one liter round bottom flask, equipped with a heatingmantle, Dean-Stark trap and water-cooled condenser. The mixture isrefluxed for four hours and the toluene, water and acetic acid aredistilled from the reaction product.

EXAMPLE VIII

A zinc derivative of boramid C/12 is prepared by mixing 54 grams of thereaction product of Example I (boramid C/12) with 400 ml of toluene,19.1 grams of zinc acetate and 50 ml of methanol in a single-necked, oneliter round bottom flask, equipped with a heating mantle andwater-cooled condenser. The mixture is refluxed for four hours and thetoluene, methanol, water and acetic acid are distilled. The resultingproduct is suitable for use as an extreme pressure, anti-wear, frictionreducing additive for lubricating compositions.

EXAMPLE IX

A metal boramid is prepared by following the procedure of Example VIIwith the following exception: zinc acetate is substituted for the nickelacetate to produce zinc-boramid T/12.

It is to be noted that transition metals having an atomic number between21 and 30, and Group IVA metals of the Periodic Table may be substitutedfor the nickel and zinc metals herein to prepare corresponding metalboramids.

EXAMPLE X

The extreme pressure, anti-wear and friction reducing additives, boramidC/12 and nickel-boramid C/12 produced in Examples I and VI in a 1:1ratio mixture are mixed with 450 neutral oil and evaluated forperformance. The additive mixture is mixed with the 450 neutral oil at 5weight percent based on the total weight of the lubricant composition.The boramid C/12, nickel-boramid C/12 and 450 neutral oil mixture iscompared to Arco graphite lubricant and ASTM high reference oil, SAE20W/30 for friction reduction and extreme pressure properties.

The above lubricant is tested in accordance with the procedure disclosedin ASTM D3233-73 (Reapproved 1978) using a Falex lubricant tester. Thetest is performed by applying resistance to a revolving metal journal.Resistance is applied by two V-Blocks equipped with a ratchet mechanismwhich steadily increases pressure on the journal. The metal journal andV-Blocks are composed of steel in this example. The metal journal andV-Blocks are submerged in the lubricating composition to be tested. Theresults are indicated in Table 1 below.

                  TABLE 1                                                         ______________________________________                                        LUBRICANT                                                                     Torque on Journal (lbs-in.)                                                                  450 Neutral Oil                                                True 450 Neutral                                                                             With Boramid C/12      ASTM                                    Load Oil - No  and Ni--Boramid C/12                                                                          Arco   SAE                                     lbs  Additives mixture (1:1 ratio)                                                                           Graphite                                                                             20W/30                                  ______________________________________                                         300  8        4                6      6                                       500 11        6                8      7                                       750 16        9               16     12                                      1000 Journal   14              21     20                                           Shear                                                                    1250 --        21              26     24                                      1500 --        Journal         Journal                                                                              Journal                                                Shear           Shear  Shear                                   ______________________________________                                    

It should be noted that substantially the same results are obtained whennickel-boramid T/12 additive is substituted for the nickel-boramid C/12additive above.

EXAMPLE XI

A boramid C/12, nickel-boramid C/12 and neutral 450 oil mixture istested in accordance with the procedure set forth in Example X with thefollowing exception: the metal Journal and V-Blocks are constructed fromcast iron. The results are indicated in Table 2 below.

                  TABLE 2                                                         ______________________________________                                               LUBRICANT                                                                     Torque on Journal (lbs-in.)                                                     450 Neutral Oil-                                                              with Boramid C/12                                                    True Load,                                                                             and Ni--Boramide                                                                             Arco     ASTM                                         lbs      Mixture (1:1 ratio)                                                                          Graphite SAE 20W/30                                   ______________________________________                                         300      3              6        6                                            500      4              7        7                                            750      7             13       10                                           1000     12             15       14                                           1250     14             17       17                                           1500     16             20       19                                           1750     18             23       21                                           2000     Journal        24       Journal                                               Wear                    Wear                                         2250     --             Journal  --                                                                   Wear                                                  ______________________________________                                    

Nickel-boramid T/12 may conveniently be substituted for thenickel-boramid C/12 above with substantially the same results.

EXAMPLE XII

A boramid C/12, nickel-boramid, 450 neutral oil mixture is tested inaccordance with the procedure set forth in Example X with the followingexception: The Journal is constructed from cast iron and the V-Blocksare constructed from chrome. The lubricant properties of the boramidC/12, nickel-boramid C/12 and 450 neutral oil mixture are compared withthose of Arco graphite and ASTM, SAE 20 W/30 lubricants. The lubricantscompositions are tested in accordance with the procedure disclosed inASTM:D3233-73 (Reapproved 1978) using a Falex Lubricant tester. Theresults are indicated in Table 3 below.

                  TABLE 3                                                         ______________________________________                                               Torque on Journal (lbs-in.)                                                     450 Neutral Oil                                                               with Boramid C/12                                                    True Load,                                                                             Ni--Boramid C/12                                                                             Arco     ASTM                                         lbs      mixture (1:1 ratio)                                                                          Graphite SAE 20W/30                                   ______________________________________                                         300     5              4         5                                            500     6              5         7                                            750     7              8        10                                           1000     12             11       14                                           1250     15             16       20                                           1500     Journal        Journal  Journal                                               Wear           Wear     Wear                                         ______________________________________                                    

EXAMPLE XIII

An extreme pressure, anti-wear and friction-reducing lubricantcomposition is prepared by mixing 5 weight percent of the zinc-boramidC/12 additive of Example VIII with 450 neutral oil. The lubricantcomposition reduces wear and friction of metal components in movingcontact with each other and, in addition, lubricates said metal surfacesunder extreme pressure or boundary lubrication conditions.

EXAMPLE XIV

The zinc-boramid T/12 additive of Example IX is admixed with 450 neutraloil at 5 percent by weight based upon the total lubricant composition toprepare an extreme pressure, anti-wear and friction reducing lubricantcomposition. The zinc-boramid T/12 additive imparts extreme pressure,antiwear and friction reducing properties to the 450 neutral,lubricating oil.

EXAMPLE XV

A lubricant composition containing nickel-boramid C/12 and 450 neutraloil are tested for extreme pressure, anti-wear and friction reducingproperties in a 1973 Chevrolet 350 cu. in. displacement V-8 engine whichis run continously for 196 hours on a single fill of the lubricatingcomposition. The lubricating oil does not contain conventional zincdialkydithiophosphate anti-wear additives. The lubricant composition isdisclosed in detail in Table 4 below.

                  TABLE 4                                                         ______________________________________                                        Compound         Weight Percent                                               ______________________________________                                        450 neutral oil  89.965                                                       Boramid C/12     2.5.000                                                      Nickel-boramid C/12                                                                            2.5.000                                                      Oronite OLOA 1200.sup.(A)                                                                      4.000                                                        Chlorowax 40.sup.(B)                                                                           1.000                                                        UNAD 242.sup.(C) 0.010                                                        Terphthalic Acid.sup.(D)                                                                       0.005                                                        Quinizarin.sup.(E)                                                                             0.020                                                        ______________________________________                                         .sup.(A) Oronite OLOA 1200  alkyl succinimide type ashless dispersant.        .sup.(B) Chlorowax 40  Chlorided paraffin containing 40% chlorine.            .sup.(C) UNAD 242  Silicone type defoamant containing kerosene.               .sup.(D) Terphthalic acid  Corrosion inhibitor.                               .sup.(E) Quinizarin  Antioxidant.                                        

The Chevrolet engine is programed to run in a repeating cycle thataveraged approximately 40 MPH. The cycle is disclosed in Table 5 below.

                  TABLE 5                                                         ______________________________________                                        Cycle   RPM        Speed (MPH)                                                                              Time (MIN.)                                     ______________________________________                                        1        700        0         2.0                                             2       1700       45         3.0                                             3       1200       30         4.0                                             4       2225       60         7/60                                            5       2400       65         3.0                                             ______________________________________                                    

After the 196 hour engine test is completed, several areas in the enginewhich are subject to wear are closely examined. These areas include:main bearings, top end bearings, cam shaft bearings, valve lifters andcham shaft lobes.

The length of the engine run is equivalent to approximately 8,000 milesof driving. A detailed examination of the above-described componentsindicated no abnormal or excessive wear.

EXAMPLE XVI

The extreme pressure, anti-wear and friction reducing additives boramidC/12 produced in Example I and boramid T/12 produced in Example II aresequentially mixed with SAE 10 W/40 motor oil.sup.(a) containing 0.15weight percent of phosphorous and 0.17 weight percent of zinc. Inaddition, the motor oil contains 0.21 weight percent of calcium.

The additive and/or lubricant composition is tested in accordance withthe procedure disclosed in ASTM D3233-73 (Reapproved 1978) using a Falexlubricant tester. The test, in accordance with the above ASTMdesignation, is performed by applying resistance to a revolving metaljournal. A rachet mechanism movably attached to two V-Blocks appliesresistance by steadily increasing pressure on the journal. The metaljournal and V-Blocks (steel) are submerged in the lubricant compositionto be tested.

                  TABLE 6                                                         ______________________________________                                        Torque on Journal (lbs.-in.)                                                  True  SAE 10W/40.sup.(a)                                                                        SAE 10W/40   SAE 10W/40                                     Load  Without     With         With                                           lbs   Additive    1% Boramid C-12                                                                            1% Boramid T-12                                ______________________________________                                          100  8           71/2         71/2                                            250 12          10            9                                               500 19          15           14                                               750 22          18           19                                             1,000 25          22           22                                             1,250 35          25           25                                             1,500 Journal     27           27                                                   Shear                                                                   1,750 --          Journal      33                                                               Shear                                                       2,250 --          --           Journal                                                                       Shear                                          ______________________________________                                         .sup.(a) Union Super Motor Oil, marketed commercially by the Union Oil        Company of California.                                                   

EXAMPLE XVII

A metal-boramid is prepared by following the procedure of Example VIwith the following changes: 31 grams of boramid C/12 is mixed with 19grams of lead (II) acetate, 150 ml. of toluene and 25 ml of methanol.The mixture is refluxed for 2 hours, after which, the toluene, methanol,water and acetic acid (produced from acetate) are distilled usingconventional techniques and apparatus. The resulting lead-boramid C/12product (32.6 grams) is a golden colored oil with the consistency ofhoney.

EXAMPLE XVIII

The extreme pressure, anti-wear and friction reducing additive,lead-boramid C/12 produced in accordance with the procedure of ExampleXVII is blended with 450 neutral oil at 5 percent by weight based on thetotal weight of the lubricant composition. The above, lubricantcomposition is compared to Arco graphite lubricant and ASTM highreference oil, SAE 20W-30 for friction reduction and extreme pressureproperties:

The lead-boramid C/12 and 450 neutral oil mixture is compared to Arcographite and ASTM, SAW 20E-30 in accordance with the procedure disclosedin ASTM:D3233-73 (Reapproved 1978) using a Falex Lubricant tester. Thetest is performed by applying resistance to a revolving metal journal.Resistance is applied by two V-Blocks equipped with a ratchet mechanismwhich steadily increases pressure on the journal. The metal journal andV-Blocks are composed of steel in this example. The metal journal andV-Blocks are submerged in the lubricating composition to be tested. Theresults are indicated in Table 7 below.

                  TABLE 7                                                         ______________________________________                                               Torque on Journal (lbs.-in.)                                           True Load                                                                              450 Neutral Oil with                                                                         Arco     ASTM SAE                                     (lbs)    Lead-Boramid C/12                                                                            Graphite 20W - 30                                     ______________________________________                                         300      7              6        6                                            500     11              8        7                                            750     14             16       12                                           1000     20             21       20                                           1250     23             26       24                                           1500     40             Journal  Journal                                                              Shear    Shear                                        1750     85                                                                   2000     94                                                                   2250     90                                                                   2500     71                                                                   2750     79                                                                   3000     70                                                                   3250     70                                                                          Stopped due to inability to increase load.                             ______________________________________                                    

EXAMPLE XIX

A copper-boramid is prepared by adding 62 grams of boramid C/12, 150 mlof toluene, 50 ml of water and 18.2 grams of cupric acetate to a 500ml., single necked round bottom flask equipped with a Dean-Stark trapand condenser. The mixture is refluxed for 8 hours, after which, water,toluene and produced acetic acid (from acetate) are distilled leaving 68grams of a green solid.

EXAMPLE XX

The copper-boramid C/12 additive produced in Example XIX is admixed with450 neutral oil at 5 weight percent based on the total weight of thelubricant composition and evaluated for performance in accordance withthe procedure of Example XVIII with the following exception: thelubricant properties of the copper-boramid, 450 neutral oil mixture arecompared with those of 450 neutral oil and SAE 10W-40 lubricants. Theresults are indicated in Table 8 below:

                  TABLE 8                                                         ______________________________________                                        Torque on Journal (lbs.-in.)                                                  True Load                                                                             450 Neutral Oil with                                                                         430 Neutral Oil                                                                            ASTM                                      (lbs)   Copper-Boramid C/12                                                                          Without Additive                                                                           10W - 40                                  ______________________________________                                         300     9             10           --                                         500    11             15           17                                         750    17             23           21                                        1000    20             Journal      28                                                               Shear                                                  1250    28                          33                                        1500    55                          Journal                                                                       Shear                                     1750    55                                                                    2000    55                                                                    2250    60                                                                    2500    70                                                                    2750    75                                                                    3000    80             (Stopped for inspection).                              ______________________________________                                    

As can readily be determined from the above Examples, the additivesherein impart extreme pressure, anti-wear and friction reducingproperties to lubrication compositions when used in accordance with thedisclosure herein. Obviously, many modifications and variations of theinvention, as hereinbefore set forth, may be made without departing fromthe spirit and scope thereof, and therefore only such limitations shouldbe imposed as are indicated in the appended claims.

We claim:
 1. A lubricating composition comprising a major amount of alubricating oil and a minor amount of a compound of the formula:##STR3## wherein R is hydrogen or an alkyl, aryl, alkylaryl or arylalkylradical having from 1 to about 24 carbon atoms, R' and R" are straightor branched carbon chains, aryl, alkylaryl or arylalkyl radicals havingfrom about 2 to about 20 carbon atoms, y is an integer of 1 to 4, and Xis a metal selected from a transition metal having an atomic numberbetween 21 and 30 or a Group IVA metal or a mixture thereof.
 2. Thelubricating composition defined in claim 1 wherein the compoundcomprises from about 0.5 to about 10 weight percent of boron.
 3. Thelubricating composition defined in claim 1 wherein the compoundcomprises from about 1 to about 17 weight percent of a transition metalor a Group IVA metal.
 4. The lubricating composition defined in claim 1wherein X is a member selected from the group consisting of titanium,vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, tinand lead and mixtures thereof.
 5. The lubricating composition defined inclaim 1 wherein the compound is a member selected from the groupconsisting of metal derivatives of methylaminodiethylate hydrogenborate, ethylaminodiethylate hydrogen borate, propylaminodiethylatehydrogen borate, butylaminodiethylate hydrogen borate,octadecylaminodiethylate hydrogen borate, dodecylaminodiethylatehydrogen borate and phenylaminodiethylate hydrogen borate and mixturesthereof.
 6. The lubricating composition defined in claim 5 wherein themetal of the metal derivative is a member selected from the groupconsisting of scandium, vanadium, chromium, manganese, iron, cobalt,nickel, copper, zinc, tin and lead and mixtures thereof.
 7. Alubricating composition comprising a major amount of a lubricating oiland a minor amount of a compound of the formula: ##STR4## wherein R ishydrogen or an alkyl, aryl, alkylaryl or arylalkyl radical having fromabout 1 to about 18 carbon atoms, R' and R" are straight or branchedcarbon chains, aryl, alkylaryl or arylalkyl radicals having from 2 toabout 10 carbon atoms, y is an integer of 1 to 4, and X is a metalselected from a transition metal having an atomic number between 21 and30 or a Group IVA metal or a mixture thereof.
 8. The lubricatingcomposition defined in claim 7 wherein the compound comprises from about2 to about 5 weight percent of boron.
 9. The lubricating compositiondefined in claim 7 wherein the compound comprises from about 5 to about10 weight percent of a transition metal or a Group IVA metal.
 10. Thelubricating composition defined in claim 7 wherein X is a memberselected from the group consisting of scandium, titanium, chromium,manganese, iron, cobalt, nickel, copper, zinc, tin and lead and mixturesthereof.
 11. The lubricating composition defined in claim 7 wherein thecompound is a member selected from the group consisting of metalderivatives of methylaminodiethylate hydrogen borate,ethylaminodiethylate hydrogen borate, butylaminodiethylate hydrogenborate, octadecylaminodiethylate hydrogen borate, dodecylaminodiethylatehydrogen borate, and phenylaminodiethylate hydrogen borate, and mixturesthereof.
 12. The lubricating composition defined in claim 7 wherein themetal of the metal derivative is a member selected from the groupconsisting of scandium, titanium, vanadium, manganese, iron, cobalt,nickel, copper, zinc, tin and lead and mixtures thereof.
 13. Alubricating composition comprising a major amount of a lubricating oiland a minor amount of a compound of the formula: ##STR5## wherein R ishydrogen or an alkyl, cyclic or alicyclic radical having from 1 to about24 carbon atoms, R' and R" are straight or branched carbon chains,cyclic or alicyclic radicals having from about 2 to about 20 carbonatoms, y is an integer of 1 to 4, and X is a metal selected from atransition metal having an atomic number between 21 and 30 or a GroupIVA metal or a mixture thereof.
 14. The lubricating composition definedin claim 13 wherein X is a member selected from the group consisting ofscandium, titanium, vanadium, chromium, iron, cobalt, nickel, copper,zinc, tin and lead and mixtures thereof.
 15. The lubricating compositiondefined in claim 13 wherein the compound is a metal derivative ofcyclohexylaminodiethylate hydrogen borate.
 16. The lubricatingcomposition defined in claim 15 wherein the metal of the metalderivative is a member selected from the group consisting of scandium,titanium, vanadium, chromium, manganese, cobalt, nickel, copper, zinc,tin and lead and mixtures thereof.
 17. A lubricating compositioncomprising a major amount of a lubricating oil and a minor amount of acompound of the formula: ##STR6## wherein R is hydrogen or an alkyl,cyclic or alicyclic radical having from 1 to about 18 carbon atoms, R'and R" are straight or branched carbon chains, cyclic or alicyclicradicals having from about 2 to about 10 carbon atoms, y is an integerof 1 to 4, and X is a metal selected from a transition metal having anatomic number between 21 and 30 or a Group IVA metal or a mixturethereof.
 18. The lubricating composition defined in claim 17 wherein Xis a member selected from the group consisting of scandium, titanium,vanadium, chromium, manganese, iron, nickel, copper, zinc, tin and leadand mixtures thereof.
 19. A lubricating composition comprising a majoramount of a lubricating oil and a minor amount of a compound of theformula: ##STR7## wherein R is oleyl, coco or tallow, R' and R" arestraight or branched carbon chains, aryl, alkylaryl or arylalkylradicals having from 2 to about 20 carbon atoms, y is an integer of 1 to4, and X is a metal selected from a transition metal having an atomicnumber between 21 and 30 or a Group IVA metal or a mixture thereof. 20.The lubricating composition defined in claim 19 wherein X is a memberselected from the group consisting of scandium, titanium, vanadium,chromium, manganese, iron, cobalt, copper, zinc, tin and lead andmixtures thereof.
 21. The lubricating composition defined in claim 19wherein the compound is a member selected from the group consisting ofmetal derivatives of oleylaminodiethylate hydrogen borate,cocoaminodiethylate hydrogen borate and tallowaminodiethylate hydrogenborate and mixtures thereof.
 22. The lubricating composition defined inclaim 19 wherein the metal of the metal derivative is a member selectedfrom the group consisting of scandium, titanium, vanadium, chromium,manganese, iron, cobalt, nickel, copper, tin and lead and mixturesthereof.
 23. A lubricating composition comprising a major amount of alubricating oil and a minor amount of the reaction product produced bythe steps of:(A) reacting a primary amine with an alkene oxide orepoxide to produce a precursor compound, (B) reacting the precursorcompound with boric acid to produce a boramid compound, and (C) reactingthe boramid compound with a metal selected from a transition metalhaving an atomic number between 21 and 30 or a Group IVA metal.
 24. Thelubricating composition defined in claim 23 wherein the primary amine isa member selected from the group consisting of methylamine, ethylamine,propylamine, butylamine, octadecylamine, dodecylamine, cyclohexylamine,phenylamine, cocoamine, tallowamine and oleylamine and mixtures thereof.25. The lubricating composition defined in claim 23 wherein the alkeneoxide or epoxide is a member selected from the group consisting ofethylene oxide, propylene oxide, 1,2-epoxybutane, cyclohexene oxide,cyclooctene oxide, cyclododecene oxide and 1,2-epoxybenzene and mixturesthereof.
 26. The lubricating composition defined in claim 23 wherein thetransition metal or Group IVA metal is a member selected from the groupconsisting of scandium, titanium, vanadium, chromium, manganese, iron,cobalt, nickel, copper, zinc and lead and mixtures thereof.